Diamine bridged-ring compounds

ABSTRACT

A CLASS OF 2,5-AND 2,6-DIAMINE NORBORNANES, E.G. 5(6)AMINOETHYL-2-(2-AMINOETHYL)NORBORNANE, IS PRODUCED BY THE FREE RADIAL ADDITION OF A FUNCTIONALLY SUBSTITUTE ALKANE TO THE UNSATURATED CARBON ATOMS OF A BRIDGED-RING OLEFIN. THE FUNCTIONALLY SUBSTITUTED ALKANE IS FREE OF NONBENZENOID CARBON-TO-CARBON UNSATURATION AND CONTAINS AT LEAST ONE HYDROGEN ATOM BONDED TO A CARBON ATOM WHICH, IN TURN, IS (I) A CARBON ATOM OF A FUNCTIONAL SUBSTITUENT OR (II) A CARBON ATOM IN A POSIITON ALPHA TO THE FUNCTIONAL SUBSTITUENT. THE NOBORNATES PRODUCED HAVE THE RADICAL OF THE FUNCTIONALLY SUBSTITUTED ALKANE BONDED TO THE BRIDGED-RING OLEFIN MOIETY BY A CARBON-TO-CARBON BOND. THE PRODUCTS ARE USEFUL IN THE MANUFACTURE OF POLYMERS.

United States Patent U.S. Cl. 260-563 Claims ABSTRACT OF THE DISCLOSUREA class of 2,5- and 2,6-diamine norbornanes, e.g. (6)-aminoethyl-2-(2-aminoethyl)norbornane, is produced by the free radicaladdition of a functionally substitute alkane to the unsaturated carbonatoms of a bridged-ring olefin. The functionally substituted alkane isfree of nonbenzenoid carbon-to-carbon unsaturation and contains at leastone hydrogen atom bonded to a carbon atom which, in turn, is (i) acarbon atom of a functional substituent or (ii) a carbon atom in aposition alpha to the functional substituent. The norbornanes producedhave the radical of the functionally substituted alkane bonded to thebridged-ring olefin moiety by a carbon-to-carbon bond. The products areuseful in the manufacture of polymers.

This application is a division of application Ser. No. 520,298, filed onDec. 9, 1965 now U.S. 3,492,330.

This invention relates to a process for the manufacture of substitutednorbornanes and to novel norbornanes made by such process. Mostparticularly, this invention relates to a relatively inexpensive processfor the manufacture of substituted norbornanes, particularlydisubstituted norbornanes which heretofore could only be produceduneconomically, if at all, by devious manipulation of known processes.

There has previosuly been described processes which are limited to theproduction of specific di-substituted norbornanes. For example, U.S.Pat. 2,666,748 describes the manufacture of 2,5 (or6)-di(aminomethyl)norbornane by the Diels-Alder reaction ofcyclopentadiene with acrylonitrile to formbicyclo[2.2.11-5-heptene-2-carbonitrile, followed by reaction of thisDiels-Alder product with hydrogen cyanide in the presence of cobalttetracarbonyl and triphenylphosphine. Therewas obtained 2,5 (or 6)-norbornanedicarbonitrile which, upon hydrogenation, is converted to thedi(aminomethyl)-norbornane described previously. This process isincapable of producing any other di(aminoalkyl)norbornane where theamino nitrogen is bonded directly to a primary carbon atom.

U.S. Pat. 2,956,987 describes the manufacture of 2- aminomethyl-S-(or6)-norbornanecarboxylic acid by the hydroformylation of the samecarbonitrile described in U.S. Pat. 2,666,748, followed by oxidation ofthe resulting aldehyde to produce the corresponding cyanocarboxylicacid, which after hydrogenation, provides the aforementionedaminomethylnorbornane carboxylic acid. The patents process is veryspecific with respect to the type of substitution attainable on thenorbornane ring and is incapable of providing a product where thecarboxyl group is bonded directly to a primary carbon atom.

In U.S. Pat. 2,917,490, there is described norbornane- 5(or6)-amino-2-carboxylic acid which is produced by the reaction of thecarboxylic acid hydrolyzate of the monocarbonitrile employed in theprevious two patents with a nitrile, such as hydrogen cyanide,acetonitrile or benzonitrile, in the presence of a strong acid. As aresult of this reaction there is obtained the addition of a carboxyamidogroup at the ethylenic unsaturation of the carboxylic acid which, afterhydrolysis, results in the aforementioned aminocarboxylic acid. Theprocess of that patent is only capable of producing an aminocarboxylicacid wherein the amino nitrogen, as well as the carboxyl group, arebonded to secondary carbon atoms.

In addition to the above, there is described in U.S. Pat. 3,000,864 thecompounds 5 (or 6)-hydroxynorbornane-2- carboxylic acid by a processwhich is the same as that described in U.S. Pat. 2,917,490, except thatinstead of cyanide addition, a carboxylic acid is employed, followed byhydrolysis resulting in hydroxy substitution. Such a process isincapable of producing substituents bonded to norbornane which aredirectly attached to primary carbon atoms.

There is described in U.S. Pat. 2,972,602, norbornane- 2,5 (or6)-dicarboxylic acids which are produced by the hydroformylation of theaforementioned carbonitrile, described above, resulting in theformaldehyde-substituted carbonitrile which, after oxidation, isconverted to the monocarboxy substituted norbornane carbonitrile andafter hydrolysis is further converted to the di-carboxy substitutednorbornane. This patent is limited also insofar as it is only capable ofproducing substituted norbornanes wherein the substituents are bonded tosecondary carbon atoms.

U.S. 'Pat. 3,143,570 describes another process for making the diaminedescribed in U.S. Pat. 2,666,748. The process employed in U.S. Pat.3,143,570 involves the aforementioned hydroformylation technique of thecyanonorbornane followed by reaction of the aldehyde with excess ammoniato form the Schilfs base. The resulting product is hydrogenated in thepresence of ammonia to form the diamine.

The process of this invention, in addition to its inherent novelty, isuniquely different from the above art because it is capable of providingmulti-substituted bridgedring compounds, such as di-substitutednorbornanes, wherein each substituent is bonded to a carbon atom atleast two carbon atoms removed from the other substituent, and at leastone of the substituents is in the exo configuration thereby minimizingthe extent of intramolecular reaction when the bridged-ring compoundsare utilized in polymerization reactions for which they are uniquelyequipped. In addiiton, the process of this invention producespoly-substituted bridged-ring compounds unattainable by prior artprocesses.

The process of this invention involves the free radical addition of afunctionally substituted alkane on a bridged-ring olefin. The freeradical addition'is effected by intermixture of the olefin in thepresence of the substituted alkane and a free radical initiator.

The bridged-ring olefins which may be treated in accordance with theprocess of this invention possess at least one ethylenic unsaturationand include those characterized by the formula.

wherein x, y, 2, q and p are one of the integer 0 and 1, provided that zis 0 when y is 1 and y is 0 when 2 is 1, two of the Rs, Rs, R"s, R"s, Rs, R s, R s, and R s above, when bonded to adjacent ring carbon atomsmay be interconnected valence bonds to form ethylenic unsaturation inthe ring and one or more of them may be one of hydrogen, monovalentorganic radicals and monovalent inorganic sulfur or carbonyl containingradicals, such as: lower alkyl (i.e., of from 1 to about 4 carbonatoms); phenyl, alkylphenyl wherein the alkyl has from 1 to about 6carbon atoms; carboxyphenyl; hydroxyphenyl; halophenyl (e.g., chloro,iodo, bromo, fluorophenyl); aminophenyl; cyanophenyl; isocyanatophenyl;carbamoylphenyl; alkoxyphenyl; cyano; hydroxy; hydroxryalkyl of from 1to about 8 carbon atoms; cyanoalkyl of from 1 to about 9 carbon atoms;amino; aminoalkyl of from 1 to about 8 carbon atoms; carboxy;carboxyalkyl of from 1 to about 9 carbon atoms; halo (e.g., chloro,bromo, iodo and fluoro); haloalkyls of from 1 to about 8 carbon atomsand the halo radicals are those described above; carbohydrocarbyloxy(i.e.,

o Ro ("3- wherein R is an alkyl group of from 1 to about 8 carbon atomsor phenyl); alkoxy of from 1 to about 8 carbon atoms, alkoxyalkoxy offrom 3 to about 8 carbon atoms; alkoxy(polyalkyleneoxy) of from about 5to about 1,200 carbon atoms; hydroxyalkoxyalkoxy of from 3 to about 8carbon atoms; hydroxyalkoxy of from 2 to about 8 carbon atoms;hydroxyalkoxy(polyalkyleneoxy) of from about 5 to about 1,200 carbonatoms; phenyloxy; phenylolyalkoxy of from 8 to about 10 carbon atoms;phenyloxy (polyalkyleneoxy) of from 10 to about 1,000 carbon atoms;halophenyloxy wherein the halo subare described above; hydroxyphenyloxy;carboxyphenyloxy; alkoxyphenyloxy, wherein the alkoxy moiety has from 1to about 6 carbon atoms; aminophenyloxy;

cyanophenyloxy; alkylphenyloxy wherein the alkyl moiety has from 1 toabout 8 carbon atoms; carbamoylphenyloxy; alkanoyl (e.g.,

0 II R"C wherein R" is an alkyl group of from 1 to about 6 carbonatoms); phenylcarbonyl; benzylcarbonyl; alkanoyloxy wherein the alkanoylgroup contains from 1 to about 18 carbon atoms; phenyloxy; benzoyloxy;alkylthio; phenylthio; benzylthio; mercapto; sulfo; sulfamido;1,2-epoxyalkyl containing from 2 to about 8 carbon atoms; part ofcarboanhydrides wherein two of R and R to R each joined to adjacentcarbon atoms of the bridged-ring olefin, are divalent carbonyl radicals;part of di-alkyleneoxide wherein each alkylene has from 1 to about 10carbon atoms and are joined at one free valence to oxy and the freevalences of the radical are directly bonded to adjacent carbon atoms ofthe bridgedring olefin; part of dialkylene sulfide, dialkylene sulfoxideand dialkylene sulfone wherein each alkylene has from 1 to about 10carbon atoms and the free valences of the radical are directly bonded toadjacent carbon atoms of the bridged-ring olefin; part of oxydicarbonylwherein its free valences are directly joined to adjacent carbon atomsof the bridged-ring olefin; part of alkylene of from 2 to about 8 carbonatoms where its free valences are bonded to adjacent carbon atoms of thebridged-ring olefin; part of alkenlylene of from 2 to about 8 carbonatoms where its free valences are bonded to adjacent carbon atoms of thebridged-ring olefin; carboxamide; alkamido of from 1 to about 9 carbonatoms; phenylamido; benzylamido; chloroformyl; part of imidodicarbonylWhere the free valences are bonded to adjacent carbon atoms of thebridge-ring olefin; keto; part of alkylenone of from 1 to about 8 carbonatoms where the free valences are bonded to adjacent carbon atoms of thebridged-ring olefin; part of dicarbonyl alkylene of from 3 and 4 carbonatoms Where the free valences are bonded to adjacent carbon atoms of thebridged-ring olefin; part of dioxyalkylene of from 2 to about 8 carbonatoms where each oxygen is directly bonded to the same carbon atom ofthe bridged-ring olefin; thio; part of methylene where the carbon isdouble bonded to a carbon atom of the bridged-ring olefin; part ofalkylmethylene, dialkylmethylene, alkylphenylmethrylene,benzylalkylmethylene (where the alkyl groups have from 1 to about 8carbon atoms), phenylmethylene, diphenylmethylene, benzylmethylene,dibenzylmethylene and phenylbenzylmethylene wherein the methylene moietyis double bonded to a carbon atom of the bridged-ring olefin; part ofisonitroso where the nitrogen is double bonded to a carbon atom of thebridged-ring olefin; dialkoxyalkyl of from 3 to about 9 carbon atoms;alkylenedioxyalkyl of from 3 to about 7 carbon atoms; parts ofoxycarbonyl wherein its free valences are directly bonded to adjacentcarbon atoms of the bridged-ring olefin; part of dialkyleneoxycarbonylof from 3 to about 8 carbon atoms where its free valences are directlybonded to adjacent carbon atoms of the bridged-ring olefin; divalentalkylene carbonyloxy and carbonyloxyalkylene where the alkylene grouphas from 1 to about 6 carbon atoms and the free valences are joined toadjacent carbon atoms of the bridged-ring olefin; part of divalent oxywhere each free valence is joined to adjacent carbon atoms of thebridged-ring olefin; glycidyloxy; and the like.

Illustrative examples of radicals representing one or more of the Rs,|Rs, Rs, R"s, R s, R s, R s, and R s include: methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, sec.-butyl, t.-butyl; 4-methylphenyl,4-ethylphenyl, 3-isopropylphenyl, 2-isobutylphenyl, 2,4-dimethylphenyl,and the like; 4-carboxyphenyl, 3,5-dicarboxyphenyl, and the like;4-hydroxyphenyl, 3,5 dihydroxyphenyl, 3,4,5 trihydroxyphenyl, and thelike; 4-chlorophenyl, 4 bromophenyl, 3 fluorophenyl, 2,4-dichlorophenyl,4 iodophenyl, 2,3,4,5,6 pentachlorophenyl, and the like; 4 aminophenyl,3,5 diaminophenyl, 4- aminomethylphenyl, 4 gamma-amino-propylphenyl, andthe like; 4 cyanophenyl, 3,5 dicyanophenyl, 2,4-dicyanophenyl, and thelike; 2,5 diisocryanato-4-methylphenyl, 4-isocyanatophenyl, and thelike; 4 carbamoylphenyl, 2,5 dicarbamoyl 4 methylphenyl, and the like; 4methoxyphenyl, 2,4 diethoxyphenyl, 4-methoxy- 3,5-diethoxyphenyl, andthe like; Z-hydroxyethyl, hydroxymethyl, 4 hydroxybutyl, 1,2dihydroxyethyl, 6- hydroxy 2 ethylhexyl, and the like; cyanomethyl, 2-cyanoethyl, 5-cyanohexyl, and the like; aminomethyl, 3- aminopropyl, 8aminooctyl, and the like; 2-carboxyethyl, 4 carboxypentyl, and the like;chloromethyl, bromomethyl, iodomethyl, fiuoromethyl, dichloromethyl,trichloromethyl, perchloropropyl, perfluorobutyl, 2- chloro-1,2tetrafluoroethyl, and the like; carboethoxy, carbomethoxy,carbocyclohexyloxy, carbophenyloxy, and the like; methoxy, ethoxy,isopropoxy, n-propoxy, hexoxy, and the like; methoxyethoxy,methoxypropoxy, methoxyisopropoxy, ethoxybutoxy, and the like;

onlomo omoflo and the like; hydroxyethoxy, hYdIOXIYlSOPI'OPOXY, hy-

droxy-n-propoxy, and the like; hydroxyethoxyethoxy, hy-

droxyisopropoxyisopropoxy, and the like;

0( 2 2 )2me001 O 2C 2 2 )2m4t0 and the like; phenyloxyethoxy,phenyloxyisopropoxy, and

the like; 4 carbamoylphenoxy, and the like; acetyl, propionoyl, benzoyl,phenylacetyl, and the like; acetyloxy, propionyloxy, benzoyloxy,phenylacetyloxy, and the like, methylthio, n-hexylthio, and the like;ethylsulfamido, and the like; 1,2 epoxyethyl, 7,8-epoxy-n-octyl, 3,4epoxy-n-hexyl, and the like; dimethyleneoxide, diethyleneoxide,methylene ethyleneoxide, and the like; dimethylene sulfide, diethylenesulfoxide, methylene ethylene sulfone, and the like; ethylene,tetramethylene, and the like; propenylene, 3-n-hexylene, and the like;acetamido, butyramido, and the like; trimethylen 2 one, pentamethylen-2one, and the like; tetramethylen-1,4- dione, heXamethylen-1,6-dione andthe like; dioxyethylene, dioxypropylene, and the like; methylmethylene,dimethylmethylene, methylethyl methylene, phenylmethylene, methylphenylmethylene, diphenylmethylene, methylbenzyl methylene, dibenzylmethylene,and the like; dimethoxymethyl, diethoxymethyl, dibutoxymethyl,1,1-dimethoxyethyl, and the like; 1,2-ethylenedioxymethyl, 1,2-ethylenedioxy-l-ethyl, and the like; di(methylene)oxycarbonyl,methyleneoxycarbonyl, methylenecarbonyloxy, di(ethylene)oxycarbonyl, andthe like.

The aforementioned bridge-ring compounds are obtained easily byclassical reactions such as by a Diels- Alder reaction betweencyclopentadiene or substituted cyclopentadiene and an ethylenicallyunsaturated compound which may or may not bear the aforementionedsubstituents. The following table illustrates the type of productsproduced. It must be borne in mind that the following is not intended torestrict the scope and number of bridged-ring compounds usable in thepractice of this invention.

TABLE Ethylenically unsaturated Bridged-ring Cyclopentadieue compoundcompounds on m cit -circa 011 011 U CH CH CHQDR mama m ca =cu cooa mCOOCH m Wo s toc rr ci-r cn (oca cn oa CH m we 3 c =0 coon cooa cuo OHca -ca-cao f /OCH3 ca fls CH3 m cH =c(ca fi m OH G CH CyclopentadieneTABLE-Continued Ethylenically unsaturated compound Bridged-ringcompounds HOCH CH OliI-Q ca es-n on on-cu CHECK TABLECont-lnuedEthylenically unsaturated Bridged ing (lyclopentadlene compoundcompounds m a ooze QCOZCKE; weep;

As mentioned previously, this invention involves the addition offunctionally substituted alkanes in the bridged ring olefin at theunsaturation thereof. The term functionally substituted alkanes asemployed herein and in the claims, encompasses those compounds free ofnonbenzenoid carbon to carbon unsaturation and which contain at leastone hydrogen atom bonded to a carbon atom which in turn is a carbon atomof a functional substituent or a carbon atom in a position alpha to afunctional substituent. Illustrative of the term functional substituentor functionally substituted, as employed herein and in the claims, arethe following: hydroxyl, cyano, carboxy, hydrocarbyloxycarbyl, amino,oxy, dicarboanhydride, formamido, carboxamido, phenyl, substitutedphenyl (wherein the substituents are alkyl (1 to about 20 carbon atoms)halo (as described above), hydroxy, carboxy, cyano, amino, alkoXy (1 toabout 4 carbon atoms) carbamoyl, and the like.

Apart from the functional substituents, these compounds are typicallycomposed of carbon and hydrogen, and in many cases, oxygen also.Illustrative functionally substituted alkanes suitable in the practiceof this invention include, by way of example only, the following: alkyland alkylene alcohols, such as methanol, ethanol, isopropyl alcohol,isobutyl acohol, cyclohexanol, benzyl alcohol, benzhydryl alcohol,ethylene glycol, 1,2-propylene glycol, 1,4-butane diol, glycerol, andthe like; cyanides, such as methyl cyanide, ethyl cyanide, isopropylcyanide, benzyl cyanide, cyclohexyl cyanide, malononitrile, cyanohydrin,and the like; carboxylic acids, such as acetic acid, propionic acid,butyric acid, 1,4-cyclohexanedicarboxylic acid, isobutyric acid,phenylacetic acid, cyclopentylcarboxylic acid, malonic acid, succinicacid, glutamic acid, adipic acid, stearic acid, lactic acid,1,4-bis(carboxypropyl)benzene, glycine, and the like; carboxylic esters,such as ethyl acetate, methyl isobutyrate, methyl acetate, isopropylisobutyrate, ethyl phenylacetate, methyl cyclo hexylcarboxylate,dimethylmalonate, dineopentyladipate, diethyl succinate, and the like;amines, such as methylamine, trimethylamine, diethylamine,cyclohexylamine, benzylamine, n-butylamine, ethylenediamine,diethylenetriamine, morpholine, hexamethylenediamine, ethanolamine,diethanolamine, piperazine, methylolamine, N,N',N"-trimethylmelamine,N,N,N"-trimethylolmelamine, and the like; epoxides and ethers such asdiethyl ether, dimethyl ether, ethylene oxide, propylene oxide,1,4-dioxane, epichlorohydrin, tetrahydrofuran, phenyl isopropyl ether,phenyl methyl ether, dimethyl ether of ethylene glycol, dimethyl etherof dipropylene glycol, hydroXy-terminated polyalkylene oxides (e.g.,polyethylene oxide), and the like; anhydrides such as acetic anhydride,diisobutyric anhydride, succinic anhydride, benzoic acetic anhydride,and the like; formamides, such as formamide, methyl formamide, diethylformamide, dimethyl formamide, phenyl formamide; formic acid andderivatives, such as methyl formate and phenyl formate; amides, such asacetamide, n-propionamide, n-butyramide, isopropionamide,isobutyrarnide, adipamide, succinamide, N-methylacetamide,N,N-diethylacetamide, ethylene bis-acetamide, N,N-diethyladipamide,ethylene bis(isobutyramide), and the like; phenyl derivatives, such asmethylbenzene, ethylbenzene, isopropylbenzene, n-octylbenzene,n-laurylbenzene, bisphenyl methane, bis (4-phenyl) -1-ethane,1,4-dimethylbenzene, l,3,5,-trimethylbenzene, 4-carboxytoluene, 4-chlorotoluene, 2,4-dichlorotoluene, 3-trifiuoromethylcumene,4-methylphenol, S-methylpyrogallol, 4-methylbenzoic acid,S-methylphthalic acid, Z-methylterephthalic acid, 4-cyanotoluene,3-methylaniline, 4-methoxytoluene, 3-n-butoxycumene, Z-methylolphenol,3-carbamoyltoluene, N-methylcarbamoyltoluene, N-phenylcarbamoyltoluene,N-phenyl-N-methylcarbamoyltoluene, 2,4-toluenedi isocyanate, and2,6-toluenediisocyanate (and mixtures of toluene diisocyanates).

It is to be appreciated from the above that the term a functionallysubstituted alkane (or alkane for brevity) is not intended to beconstrued as simple alkane bearing a functional substituent, but ratheris intended to mean herein and in the claims to be a functionallysubstituted organic compound free of ethylenic and acetylenicunsaturation and containing a carbon atom having a hydrogen atomdirectly bonded thereto which carbon atoms is in one of the followingpositions: (1) the position alpha to the functional substituent wherethe substituent is free of such a carbon atom and (2) a position part ofthe functional substituent. The remainder of the organic compound maycontain any other combination of atoms. The organic compounds maycontain 1, 2, 3, 4, and more functional substituents though preferablynot more than 2 such substituents.

The aforementioned reaction occurs by way of free radical addition byintermixing at least one of the functionally substituted alkanes with atleast one of the bridgedring olefins in the presence of a free radicalinitiator, such as the conventional free radical addition catalysts sowell known in the art. The general classes of free radical initiatorsinclude peroxides, azo compounds, peresters, peracids, heat and thelike.

Illustrative of suitable initiators include the following:

peroxide compounds such as tertiary butyl hydroperoxide,

di-tert.-butyl peroxide, di-tert.-amyl peroxide, lauroyl peroxide,benzoyl peroxide, cumene hydroperoxide, dicumyl peroxide, hydrogenperoxide, tert.-amyl hydroperoxide, tert.-hexyl hydroperoxide, diacetylperoxide, as well as many others; azo compounds such asazo-bis-isobutyronitrile, abo-bisisoamylnitrile, azo-bisisohexylnitrile,azo-bis- 2-ethyl butyronitrile, azo-bis-2-methyl-3-phenyl propionitrile,azo-bis-Z-n-propyl amyl nitrile; peresters such as tertiary butylperacetate, cyclohexyl peracetate, neo-pentyl peracetate, peracids suchas peracetic acid, perpropionic acid, perisobutyric acid and the like.

Broadly, the function of the free radical initiator is to provide energyfor removal of a hydrogen atom from the functionally substituted alkanesdescribed above. The energy may be in the form of radical fragments fromthe initiator (as is the case with the peroxides, peracids, perestersand the azo compound) or be in the form of thermal energy.

The free radical addition reaction may be effected in liquid or vaporphase. The liquid phase reaction may be effected as a heterogeneous orhomogeneous liquid phase mixture of the component involved in theaddition reaction. Essentially all of the functionally substitutedalkanes described above are liquid at the temperature of the additionreaction and therefore can be utilized as the liquid body in which thebridged-ring olefin and the initiator is dispersed. The manner ofdispersion i.e., whether homogeneous or heterogeneous, depends on thesolvating action of the functionally substituted alkane towards thebridged-ring olefin employed, or the solvating action of thebridged-ring olefin employed toward the functionally substituted alkane.Usually, an excess of one of the functionally substituted alkane and theselected bridged-ring olefin is employed when one of them is chosen toserve as the solvating or dispersing medium.

However, other compounds which are liquid at the addition reactivetemperature may be optionally employed as a solvent for one or both ofthe prime reagents (i.e., the alkane and the bridged-ring olefins) or asa liquid dispersant for both. Illustrative of such compounds inelude, byway of example only, benzene, chlorobenzene, 1,4-dichlorobenzene,1,2-dichlorobenzene, 1,3-dichlorobenzene, nitrobenzene,1,2-dinitrobenzene, diphenylether, bis(4-chlorophenyl)ether, 1,2- and1,6-dichloronaphthalane, and the like. The selection of such solvatingor dispersing liquids is not critical except that they should beessentially inert to the free radical addition reaction and not cause anunwanted amount of reaction by-products.

In the preferred operation of this process, an excess of thefunctionally substituted alkane over the stoichiometry of the reactionis employed to provide the liquid conditions of the reaction. In themost preferred embodi ment, the reaction is carried out as a homogeneousliquid phase.

The process may also be carried out in the vapor phase where the alkaneand bridged-ring olefin is intermixed as gases in an environmentcontaining the free radical initiator. For example, a stream comprisingan admixture of the alkane and the bridged-ring olefin can be passedthrough a bed of zeolitic molecular sieves having adsorbed therein oneof the aforementioned peroxides, peracids, peresters and azo compounds.Particularly preferred, is a zeolitic molecular sieve havingdi-tert.-butyl peroxide or tert.-butyl hydroperoxide adsorbed therein.At the temperature of reaction, the initiator is desorbed from the sieveto catalyze the reaction or the reactants are absorbed into the sievewhere catalysis takes place. Usually both occurs during the reaction.

A preferred manner of carrying out the addition reaction involves addingthe bridged-ring olefin and the initiator in the initiator inincremental portions to an excess of the functionally substituted alkaneheated at the reaction temperature. The resulting addition product isseparable from the reaction system by conventional procedures such asdistillation, crystallization, solvent extraction, decantation, and thelike. Distillation is the procedure most often employed.

The addition reaction proceeds at a rate dependent upon the reactants,the catalysts, the concentrations of the reaction components, thesolvent, the temperature and the like considerations. Usually, thereaction can vary over seconds to hours depending upon the above pointsof consideration typically controlling reactions.

The reaction may proceed over a wide temperature range, but, however,the temperature of the reaction must be sufiiciently high enough tocause the initiator to provide the energy for removal of a hydrogen atomfrom the functionally substituted alkane. With respect to the compoundswhich are free radical initiators, the temperature should besufficiently high to cause their decomposition into free radicalfragments. Depending upon the free radical initiator employed, thetemperature of the reaction may range from about 10 C. up to about 250C., preferably from about 30 C. to about 200 C. In the usual case, thetemperature employed is between about C. and about 180 C., inclusive,and more preferably, between about C. and about 160 C., inclusive. Themost preferred operating temperature ranges from the standpoint of rateand yields is between about C. and about C., inclusive.

The proportion of the functionally substituted alkane to thebridged-ring olefin may vary considerably, but CN CHQOH f -CO2OH3 forbetter yields of reaction product it is desirable to NCC 11 002043employ a molar ratio of the functionally substituted Hzo'msot alkane tothe bridged-ring olefin of at least about 0.1. This molar ratio may beas large as 500, or more. Prefer- Methyl 5(01' h g f g g f' ably, themolar ratio of the alkane to the bridged-ring (aa' lsu S u e ace a eolefin is between about 0.5 and about 500, inclusive, and, mostdesirably,-between about 2 and about 300, R01 1 inclusive. In the mostpreferred embodiment, where optil z Peroxide f C02H mum yields are mostoften attainable, the molar ratio is G -ON G typically between about toabout 200. R02 A The amount of free radical initiator necessary is thatI l l catalytically effective amount Which causes the free radical6)'cal'boxynorbmnanez(""a'dlsubstituted)acetmmle addition reaction toproceed. In the case of the free radical initiating compounds, the usualcatalytic quantities are employable. Typical catalytic quantities ofthese com- 01 pounds may range from about 0.01 mole percent to equal NCI CO2H a molar quantities based on the molar amount of the Low press?bridged-ring olefin undergoing reaction. Preferably, there is employedfrom about 5 to about 50 mole percent of the compound, based on themolar amount of the bridged-ring olefin undergoing reaction, and themost C0211 desirable amount of the compound is from about 20 toH2NCH2*(|3 about 40 mole percent, based on the moles of the Rbridged-ring olefin undergoing reaction.

The process, when carried out in liquid phase, may be under anyatmosphere, though preferably under an inert atmosphere such asnitrogen, carbon dioxide, argon, heli- 5(01 6) -carboxy-2-(1,1-disubstituted2-aminoethyl) norbornane um, and the like. In a vaporstate reaction, the atmosphere 0t0Hi ii Peroxide should be inert. Thismay be accomplished by maintaining 3 EE-ON the reactant vapors as thetotal atmosphere or by feed- R02 V ing an inert gas or gases, such asthe above inert gases, to the reaction zone.

The pressure at which the reaction proceeds is not CO2OH critical.However, when the alkane is gaseous at the re- No-o CH; actiontemperature, it is preferable to employ superatmospheric pressureconditions. Subatmospheric or atmospheric pressures may be employedinstead, but are desirggi1$ ;g gg ggzggg figgfifl ably utilized when allof the reactants are liquid at the 40 operating temperature. In vaporphase reactions, pressures ranging from subatmospheric tosuperatmospheric may R01 be employed. i 2 2 Hz, cat,

Typical of the functionally substituted bridged-ring 3 Low ressumcompounds obtained by the process of this invention and 02 p the mannerby which they are obtained are illustrated by the following:

:COQCH; CN Peroxide CN H N-CH;O on.

+ CH-ON NC--C R02 1 102 Methyl 5'( or 6) 1,1-disubstituted-2-aminoethyl)-2- 5(01: 6 -Cyanonorbornane-2 a,adisubstituted) -acetonitrilemethylnorbmane2'carbxy1ate 1 Ni/NH CHZOH Peroxide NC-C H OHON l-PrOH A302 R02 CH NH 2 2 OH on H N-CH -o 2 2 2 l NC-C R02 5 6 -Am'n 0meth 1-2-1,1-disubstitutedl-2-aaninoeth l) (01 1 y nt rborn'ane y 5(0r6)-Hydroxymethylnorbomane-2-( a,a-disubstitnted) acetonitrile CH NH CHOH H R01 2 EN on o 2%, Ni/NHa 2 R i-PrOH R01 f -OH2NCO I -0H.on OCN-CH2CHgCHg-C 5(01' '6) -Is0cyanatomethyl-2- (1,1-disubstituted-2-iso- '5 or6) -Hydroxymethyl-2- (1,l-disubstituted-Z-aminoethyl)cyanatoethyhnorbornane norbornane R01 wherein the alkyl moiety has from1 to about 8 carbon Peroxide atoms; carbamoylphenyloxy; alkanoyl (e.g.,

2 CH-CzGH3 *4 O R A A RM 5 R C R01 wherein R" is an alkyl group of from1 to about 6 carbon (3 CO2OH3 atoms); phenylcarbonyl; benzylcarbonyl;alkanoyloxy 0113010? R0? wherein the alkanoyl group contains from 1 toabout 18 R carbon atoms aphenoyloxy; benzoyloxy; alkylthio; phenyl-5,1'2(or 13)-Di(methoxycarbony1 disubstituted methyl)penta 10benzyltlno; mercapto; sulfo; 'Sulfamldo;

cyclo [9 2 14,7 02,10 0s,s t t alkyl contalnlng from 2 to about 8 carbonatoms. R01 Particularly desirable substituted norbornane com- Peroxidepounds are produced in the following manner: I 2 011-00 11 A R 1 5Peroxide CHZCCMH R01 CH3CO2H w I -o-0o n A Ho,o o

H Peroxide CH1CN 5,11(0r 12)-Dl(earboxy disubstitnted methyhpentacyclo CQCN TBP [8.'2.1.1 "'.0 .0 dodecane A oN -cn CN TBP 2 \CH GN w CHQON No AA R R01 R l I ('3 CN CH ON Ni/NHZ NC-C NO H2 l i-PrOH 5,'11(0r12)-Dl(eyano disubstituted methyl)pentacycl 0 [8,2. .1 .0 -.0 ]dodecaneOH2-CH2NH2 H2NCH H lNi/NH:

1 R01 -oH2on2NH2 I -COH NH 40 H N-OH 00012 n N-orn-o 5,11(orl2)-Di(a,a-disubstituted ;5-aminoethyl)pentacyclo CH2CH2NC0 [8.2.1.1 .0.0 ]dodecane OCNCH R and R" may be hydrogen or an organic radical, suchas the following illustrative radicals: lower alkyl CH CN b t4 arbon atos hen l' alk l 1 H0 (1e,offrom1toaou c m),p y, y NC +CH3OH phenylwherein the alkyl has from 1 to about 6 carbon HZSO;

atoms; carboxyphenyl; hydroxyphenyl; halophenyl (e.g.,

chloro, iodo, bromo, fiuoro-phenyl); aminophenyl; cyanophenyl;isocyanatophenyl; carbamoylbenzyl; alkoxyphenyl; OH CO OH cyano;hydroxy; hydroxyalkyl of from 1 to about 8 carbon 0113020 atoms;cyanoalkyl of from 1 to about 9 carbon atoms;

aminoalkyl of from 1 to about 8 carbon atoms; carboxy;

carboxyalkyl of from 1 to about 9 carbon atoms; carbohydrocarbyloxy(i.e., OO2CH3 Peroxide R CHaOH HOOH A -oo,oH 18/0 0 wherein R is analkyl group of from 1 to about 8 carbon atoms or phenyl); alkoxy of from1 to about 8 carbon Lemme HooHrt atoms, alkoxyalkoxy of from 3 to about8 carbon atoms; alkoxy(polyalkyleneoxy) of from about 5 to about 1,200carbon atoms; hydroxyalkoxyalkoxy of from 3 to about 8 hydroxyalkoxy(polyalkyleneoxy) of from about 5 to about CH2OH Peroxide CHZOH 1,200carbon atoms; phenyloxy; phenyloxyalkoxy of from CHQON A NCwCH -8 to 10carbon atoms; phenyloxy(polyalkyleneoxy) of 7 from 10 to about 1000carbon atoms; halophenyloxy carbon atoms; hydroalkoxy of from 2 to 8carbon atoms; E)

wherein the halo substituents are described above; hy- OH ondroxyphenyloxy' carboxyphenyloxy' alkoxy h l 2 N1] 2 a s P y y NC HgHgN-GHg wherein the alkoxy moiety has from 1 to about 6 carbon -Pr Hatoms; aminophenyloxy; cyanophenyloxy; alkylphenyloxy CHgCN H2O HOCHCHQOH Hgso4 CH; C O 2 CH HOCEL-t CHzOH TB P CHLOH CH30H 1100112 E CH 3 TB P C|3CO2H CHCOzH T H3 CH3 CH CH /CO2H 4002B T B P a CH3 /CHCO2H HO2CCCH H3 CHzOH T B P HOCHq CHZOH omon A ornon 'No'rn.'lBP is theabbreviation for di-tert.bwtyl peroxide (also called tent.butylperoxide).

A unique feature of the novel process herein is its capability ofproducing poly-substituted norbornane wherein at least one of thesubstituents is in the exo configuration. This means that thepoly-substituted norbornanes produced by the process of this inventionreadily enter into polymerization reactions with minimization ofinternal reaction. Moreover, the process of this invention can beemployed to make poly-substituted (particularly di-substituted)norbornane unattainable by prior art processes.

A particularly preferred embodiment of this invention involves theproduction by the process of this invention of 2,5 and/ or 2,6di-substituted norbornanes characterized by the following formula:

wherein X may be one of CR R CN CR R OH CR R CR R NHR CRIRIICORVII (CR R),,N=C=O Cm vRv! and CR R NR COR R R R R R and R may each be one ofamino, halogen (such as Cl, F, and Br), hydrogen and carbon bondedmonovalent organic radicals such as alkyl of from 1 to about 18 carbonatoms, phenyl, benzyl, cycloalkyl of 36 from about 5 to about 8 carbonatoms, carboxyalkyl of from 1 to about 10 carbon atoms,alkylcarboxyalkyl of from 2 to about 20 carbon atoms, cyanoalkyl, offrom 1 to about 10 carbon atoms, carboxyphenyl, carboxyphenylalkyl,wherein the alkyl radical contains from 1 to about 6 carbon atoms,aminoalkyl of from 2 to about 10 carbon atoms, carbarnoylphenyl,phenylcarbamoylphenyl, halophenylcarbamoylphenyl,7-naphthylcarbamoylphenyl, carbamoylalkyl of from 1 to about 9 carbonatoms, phenyl carbamoyl alkyl wherein the alkyl radical has from 1 toabout 8 carbon atoms, isocyanatoalkyl of from 2 to about 7 carbon atoms,isocyanatomethylphenyl, isocyanatophenyl, isocyanatophenylmethylphenyl,hydroXy-alkyl of from about 1 to 10 carbon atoms, hydroxyalkoxyalkyl offrom about 3 to 5 carbon atoms, hydroxyphenyl, hydroxyphenylalkylwherein the alkyl radical contains from 1 to about 5 carbon atoms,hydroxylpolyalkyleneoxyalkyl containing from 2 to about 20 alkyleneoxyradicals and the alkyl radical contains from 1 to about 4 carbon atoms,alkoxyalkyl containing from about 2 to about 11 carbon atoms,alkoxypolyalkyleneoxyalkyl containing from 2 to about 20 alkyleneoxyradicals and the alkyl radicals contain from 1 to about 4 carbon atoms,vicinalepoxyalkyl wherein the alkyl radical contains from 2 to about 8carbon atoms, haloalkyl wherein the alkyl contains from 1 to about 8carbon atoms and the halo radical is at least one of chloro, iodo,bromo, and fluoro, halo substituted phenyl wherein the halosubstituent(s) is one of chloro, iodo, bromo, and fiuoro and from 1 to 5halo substituents are substituted on said phenyl radical, haloalkylphenyl wherein the halo is one of those described above and the alkylradical contains from 1 to about 4 carbon atoms, and the like organoradicals; and Y may be one of X with the exception of CR R OH and CN,OH, CR R NHR COR and wherein R may be one of chlorine, hydroxyl, alkoxyof from 1 to about 18 carbon atoms, phenyloxy, benzyloxy, cycloalkyloxyof from about 5 to about 8 carbon atoms, alkali metal oxide (such aslithium, sodium, potassium, cesium, rubidium), NH+ quaternary ammoniumoxide (+NR O, wherein R is alkyl of from 1 to about 4 carbon atoms,phenyl and benzyl), and the like radicals; and n is one of the integers1 and 2.

The compounds encompassed by Formula II are formed by the Diels-Alderreaction between cyclopentadiene and a functionally substitutedethylenically unsaturated compound to produce 2-functionallysubstituted-S-norbornene followed by adding an aforedefined functionallysubstituted alkane to the functionally substituted norbornane by theabove described process.

To illustrate, cyclopentadiene, i.e.,

can be reacted with a functionally substituted ethylenically unsaturatedorganic compound, such as OH =CHCN, OH CHCH CN, CHFCICN, CH2=CHC|HCNCHzCN CH2=CHCHCN, CHFCHCHCN, CHz=CHCHzCOOH JgHs CH CHCHCOOIT,CH2=CIICHBFCOOIL CIT CIICI-ICOOH I CH CEHIJHO OH, CHz=CHCFzCOOH,CHFOHCIJO O OH I Cl I CHg -(EHCOOOH, OHz=CHCH OH, CHFCHOIIhQ-OH COOH COOH CH2CH2 CH CH(I3HC O OH, CH2=CHCHCH /CH;

(1112 CHI-CH CH CH CHFCHCHCOOH,

J CH2=CHCHCOOH, CH:=CHCOOCH 1 0:

CHzCHzCN CHFOHC 0 0 0 1112, CH =CHO O 0 CGH5 (hexylaerylate) (phenylacrylate) CH CHCOOCHZC 2CH2, CH =OHCOONH CH =CHCH COONa,CH2=CHCH2COON(CH3)4,

CHF CHCHQCO OCHa- CH:CH2 (1H CHFCHCEECOOCH CH CH2=CHCHCOOH CH C 2 I C OO olflHgl (decyl ethyl-2-vinyl malonate) CH OHCHCOOCH CH =CHCHCOOC H I ICH2 N I IYIH I C O O 000- CH =CHCHOO O CH dition reaction with thenorbornenes to produce the compounds of Formula II include, for example,the following:

CHaCHzOOCCHgCO o omens omooorr,

HOOCCH OHZCOOH, HZNCHZCHECHZCOOH,

The novel disubstituted norbornane compounds defined by Formula II finda variety of uses and are particularly suitable in the manufacture ofpolymers which in turn can be used in the manufacture of fibers, films,coatings, molded objects, castings, and plasticizers. The polymers thatare produced from the novel norbornanes depicted by Formula II aretypically those which involve a condensation reaction or an additionreaction of the urethane type, viz, the reaction of an iscyanate and anactive hydrogen compound, as determined according to the Zerewitinolfmethod described in the Journal of the American Chemical Society, volume48, page 3181 (1927). The polymers possess the recurring unit,

III

i.e., the divalent norbornylene radical, within its internal structure.

The functional substituents on the norbornane ring determine the type ofpolymer which is formed. For example, if the functional substituentsbear isocyanato radicals, the novel substituted norbornanes may beemployed in the manufacture of polyurethanes, polyureas, mixtures ofpolyurethanes and polyureas, and 1,l-addition polyamides by reactionwith itself or other isocyanates. The novel norbornanes bearing at leastone carboxyl group may be employed in the manufacture of polyestercompositions, polyamide compositions, as hardeners in the curing ofepoxy compositions, and the like. The novel norbornane compoundsencompassed by Formula II which contain at least one amido group, may beemployed as a reactant to make polyamides, polyureas, act as aconventional amine hardener for epoxy resins, as reactant with alkyleneoxides to form a polyalkylene amide adduct, as a reactant with aldehydesto form amine-aldehyde resins, and the like. The novel norbornanecompounds which contain at least one hydroxyl group can be employed tomanufacture polyesters, polycarbonates, alkylene oxide adducts,polyurethanes, and the like. The novel norbornane compounds withinFormula II which bear at least one oxirane group may be employed in theformation of epoxy resins by acid or alkaline hydrolysis or by reactionwith conventional epoxy hardeners, or may be employed as a precursor forhydroxyl-containing monomers by simple hydrolysis of the oxirane group.

The novel carbamates esters encompassed by Formula II (including thecarbamic acid derivatives) may be employed in a manner similar to thecarboxy derivatives described above to form polyureas, polyurethanes,and the like.

Thus, the divalent norbornane radical is joined through a linkage toother segments of the polymer structure. Such linkages include, by wayof example, the ester linkage,

that is, a linkage formed by joining the free valences of a carbonyloxyradical to carbon atoms; a carbonamide radical (CONH) where the freevalences thereof are joined to carbon atoms; oxy radical, that is, anether oxygen group where the divalence of the oxygen is directly joinedto carbon atoms; urethane linkages, i.e.,

where the free valences thereof are joined directly to carbon atoms;urea linkages, i.e., NHCONH-, where the free valences are directlyjoined to carbon atoms.

Such linkages are separated typically from the norbornane radical by atleast one carbon atom which is directly joined to the norbornyleneradical III.

The following discussion of specific illustrations of the types ofpolymers producible from the 2.5 and/or 2-6- norbornanes of Formula IIis regarded only as illustrative of the products embraced by thisinvention and is not intended to limit the scope of this invention.

The diisocyanates of Formula II, illustrated by may be reacted withactive hydrogen containing compounds such as a polyol such as those ofthe following formula:

wherein A may be a radical such as Q is bonded to A by an ether (O-)bridge of an oxyalkylene radical and is at least one oxyalkyleneradical, preferably at least two recurring oxyalkylene radicals, saidoxyalkylene moieties having from 2 to 18 carbon atoms, preferably from 2to 8 carbon atoms; 2 is one of and an integer of at least 1; v is aninteger equal to the free valence of the radical A minus the value of p;each R,

R and R may be one of hydrogen, an alkyl group of from 1 to 18 carbonatoms, preferably from 1 to 4 carbon atoms, cycloalkyl of from 5 to 7carbon atoms, or an aryl group; is an integer of from 1 to 10; m is aninteger of from 0 to 8; g can be an integer of from 1 to 10; h can be aninteger of from 1 to 8; x is one of the integers 0 to l; t is an integerof from 2 to 4; c is a number having an average value of at least 2; Mis a radical which can be alkyl, aralkyl,

KIT... \1 J.

0 is one of the integers O to 1; B is hydrogen or an alkyl group of from1 to 4 carbon atoms; L is B or wherein the free valence of is thevalence bond of L; d, d and d" are each equal to 4 to 10: f is either avalue of 0 to 1; and D is methyl when f is 0 and hydrogen when 1 is l.

Polyols encompassed by the above Formula IV include those formed by theaddition of alkylene oxides to an initiating polyhydroxy substitutedorganic compound in which the hydroxy substituents are bonded to carbonof the organic compound and the initiating polyhydroxy substitutedorganic compounds.

The result of such addition forms a hydroxylated alkylene oxide adductof said hydroxy substituted organic compound. Thus, various 1,2-alkyleneoxides such as ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide,1,2-hexylene oxide, 1,2-dodecylene oxide, cyclohexyl ethylene oxide, andstyrene oxide, or mixtures thereof, may be polymerized by contact with abasic or acidic catalyst in the presence of the initiating polyhydroxyorganic compound. The aforementioned 1,2-alkylene oxides may becopolymerized with 1,3- and 1,4-alkylene oxides by acid catalyticpolymerization in the presence of the initiating polyhydroxy organiccompound. Illustrative of various 1,3- and 1,4-alkylene oxides include1,3-propylene oxide, 1,4-butylene oxide (tetrahydrofuran), 1,4-pentyleneoxide, 1,4-octylene oxide, etc., and 1,4-epoxy-2-phenyl butane, and thelike. The 1,3- and 1,4-alkylene oxides may be reacted above with theinitiating hydroxy compound to form useful polyols.

The initiating polyhydroxy organic compound include by way of example1,2-alkylene glycol, 1,3-alkylene glycol, 1,4-alkylene glycol, alkylenetriols, alkylene tetrols, alkylene pentols, alkylene hexols,polyalkylene gycols, etc. Illustrative of these materials include,ethylene glycol, 1,2- and 1,3-dihydroxypropane, 1,2-, 1,3-,1-4-dihydroxypentane, 1,2-, 1,3-, 1,4-dihydroxyhexane 1,2-, 1,31,4-dihydroxydecane, 1,2-, 1,3-, 1,4-dihydroxyoctadecane, and the alpha,omega diols of the above hydrocarbon moieties not indicated as such.Polyalkylene glycols include, diethylene glycol, triethylene glycol,tetraethylene glycol, 1,2- and 1,3-dipropylene glycol, 1,2- and1,3-tripropylene glycol, 1,2-, 1,3- and 1,4-dibutylene glycol, 1,2-,1,3- and 1,4-tributylene glycol, etc. Triols which may be utilized asthe initiating hydroxy organic compound include, glycerol,1,1,1-trimethylolpropane, 1,2,3-trihydroxybutane,1,2,3-trihydroxypentane, 1,2,3-trihydroxyoctane, 1,2,3-trihydroxydecane,1,2,4-trihydroxybutane, 1,2,4-trihydroxyhexane, 1,2,6-trihydroxyhexane,1,2,8-trihydroxyoctane, and the like. Illustrative of other polyolswhich are suitable initi-

